JP3649953B2 - Active material, electrode, non-aqueous electrolyte secondary battery, and method for producing active material - Google Patents
Active material, electrode, non-aqueous electrolyte secondary battery, and method for producing active material Download PDFInfo
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- JP3649953B2 JP3649953B2 JP17697499A JP17697499A JP3649953B2 JP 3649953 B2 JP3649953 B2 JP 3649953B2 JP 17697499 A JP17697499 A JP 17697499A JP 17697499 A JP17697499 A JP 17697499A JP 3649953 B2 JP3649953 B2 JP 3649953B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
【０００１】
【発明の属する技術分野】
本発明は、非水電解液二次電池の正極に用いて好適な活物質、その活物質を有する電極、その電極を用いた非水電解液二次電池、及び活物質の製造方法に関する。
【０００２】
【従来の技術】
従来、非水電解液二次電池としては、リチウムの吸蔵、放出が可能な正極及び負極と、非水電解液とを備えたものがある。
【０００３】
このような非水電解液二次電池は、正極活物質として、リチウムと、ニッケル、コバルト等の金属との複合酸化物であるリチウム含有複合酸化物を用いられており、約４Ｖの電圧を持ち高容量であることから、活発な研究開発が行われている。
【０００４】
しかしながら、上述した従来の非水電解液二次電池では、保存時において、正極と電解液との反応により、保存特性が劣化するという問題がある。
【０００５】
このような問題を解決するものとして、例えば、特開平９−２４５７８７号公報において、硫酸根（ＳＯ4）を含有した正極活物質が提案されている。
【０００６】
しかしながら、このような正極活物質を用いた非水電解液二次電池においても、放電容量が低下し、保存特性は満足出来るものではない。
【０００７】
【課題を解決するための手段】
本発明の活物質は、ＬｉＮｉaＣｏbＭcＯ2（但し、０≦ａ＜１、０≦ｂ＜１、ａ＋ｂ＋ｃ＝１；０≦ｃ≦０．５；Ｍは、Ｔｉ、Ｃｒ、Ｍｇ、Ａｌ、Ｃｕ、Ｇａの中か選ばれる少なくとも一種）に対し、ＡｌＸ（ＳＯ 4 ） 2 （Ｘは、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、ＮＨ 4 の中から選ばれる少なくとも一種）を１．５モル％以上、２０モル％以下含有させ、８０℃以上３５０℃以下で熱処理したことを特徴とする。
【０００８】
また、本発明は、非水電解液二次電池の正極として用いた場合、前記二次電池を放置した際における放電容量の低下が少なく、二次電池の保存特性を良好にするのに適した電極を提供することを目的とするものである。
【０００９】
また、本発明は、放置した際における放電容量の低下が少なく、保存特性を良好にするのに適した非水電解液二次電池を提供することを目的とするものである。
【００１０】
また、本発明は、非水電解液二次電池の正極活物質として用いた場合、前記二次電池を放置した際における放電容量の低下が少なく、二次電池の保存特性を良好にするのに適した活物質の製造方法を提供することを目的とするものである。
【００１１】
【課題を解決するための手段】
本発明の活物質は、ＬｉＮｉaＣｏbＭcＯ2（但し、ａ＋ｂ＋ｃ＝１；０≦ｃ≦０．５；Ｍは、Ｍｎ、Ｆｅ、Ｚｎ、Ｔｉ、Ｃｒ、Ｍｇ、Ａｌ、Ｃｕ、Ｇａの中から選ばれる少なくとも一種）に、ＡｌＸ（ＳＯ4）2（Ｘは、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、ＮＨ4の中から選ばれる少なくとも一種）を含有したことを特徴とする。
【００１２】
このような構成の活物質は、非水電解液二次電池の正極活物質として用いた場合、二次電池の自己放電率が小さく、二次電池の保存特性が良くなる。尚、これは、ＬｉＮｉaＣｏbＭcＯ2の活性部が減少し、正極活物質と電解液との反応が抑制され、正極の劣化が抑制されるためと考えられる。また、ＬｉＮｉaＣｏbＭcＯ2のＭの添加量によっては充放電容量が低下する場合があり、Ｍの添加量としては、０≦ｃ≦０．５の範囲が好ましい。
【００１３】
更に、本発明の活物質は、前記ＡｌＸ（ＳＯ4）2の含有量が、前記ＬｉＮｉaＣｏbＭcＯ2に対して１．５モル％以上、２０モル％以下であると、非水電解液二次電池の正極活物質として用いた場合、二次電池の自己放電率は大幅に低下する。
【００１４】
更に、本発明の活物質は、前記ＡｌＸ（ＳＯ4）2の含有量が、前記ＬｉＮｉaＣｏbＭcＯ2に対して３モル％以上、１０モル％以下であると、非水電解液二次電池の正極活物質として用いた場合、二次電池の自己放電率はより一層大幅に低下する。
また、本発明の活物質は、前記熱処理温度が１００℃以上、３００℃以下である場合、二次電池の自己放電率が大幅に低下する。
【００１５】
また、本発明の活物質は、前記ＡｌＸ（ＳＯ4）2が前記ＬｉＮｉaＣｏbＭcＯ2の表面を被覆するため、ＬｉＮｉaＣｏbＭcＯ2と電解液との反応が十分に抑制される。
【００１６】
また、本発明の電極は、上述の活物質を有することを特徴とする。
【００１７】
このような構成の電極は、非水電解液二次電池の正極として用いた場合、二次電池の自己放電率が小さく、二次電池の保存特性が良くなる。
【００１８】
また、本発明の非水電解液二次電池は、上述の電極を正極として用いたことを特徴とする。
【００１９】
このような構成の非水電解液二次電池は、自己放電率が小さく、保存特性が良くなる。
【００２０】
尚、本発明の非水電解液二次電池の電解液の溶質としては，ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣＦ3（ＣＦ2）3ＳＯ3等を使用することができるが，これに限定されるものではない。
【００２１】
また、本発明の非水電解液二次電池の電化液の溶媒としては，エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、スルホラン、１，２−ジメトキシエタン、テトラヒドロフラン、１，３−ジオキソラン等を使用することができるが，これに限定されるものではない。
【００２５】
【発明の実施の形態】
以下、本発明の実施の形態について詳細に説明する。
【００２６】
[正極活物質の作製]
ＬｉＣｏＯ2に対して、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％になるように混合し、２５０℃で２時間熱処理を行い、正極活物質を作製した。
【００２７】
[正極の作製]
上述の正極活物質と、導電剤としてのカーボン粉末と、結着剤としてのポリテトラフルオロエチレンとを８０：１０：１０の重量比で混合して正極合剤を得た。
【００２８】
次に、この混合物を加圧成形し、１００℃で２時間真空乾燥し、正極を作製した。
【００２９】
[負極の作製]
リチウム−アルミニウム合金を所定寸法に打ち抜き、負極を作製した。
【００３０】
[電解液の作製]
エチレンカーボネートとジエチルカーボネートとを体積比１：１で混合した溶媒に、ＬｉＰＦ6を１Ｍの割合で溶かし、電解液を作製した。
【００３１】
[電池の組立]
前記の負極を断面略コ字状の負極缶の内底面に固着し、前述の体積比で調製した電解液を含浸させたセパレータを介して、前記の正極を固定した断面略コ字状の正極缶を配置し、電池Ａ０を作製した。なお、セパレータとしては、イオン透過性のポリプロピレン製の微多孔膜を用いた。
【００３２】
（実験１（参考実験））
正極活物質に含有させるＡｌＸ（ＳＯ4）2の種類について、下記の電池Ａ１〜Ａ４を作製して検討を行った。
【００３３】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏ代わりに、ＡｌＮａ（ＳＯ4）2・１２Ｈ2Ｏを用いた以外は、電池Ａ０と同様にして、電池Ａ１を作製した。
【００３４】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏ代わりに、ＡｌＲｂ（ＳＯ4）2・１２Ｈ2Ｏを用いた以外は、電池Ａ０と同様にして、電池Ａ２を作製した。
【００３５】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏ代わりに、ＡｌＣｓ（ＳＯ4）2・１２Ｈ2Ｏを用いた以外は、電池Ａ０と同様にして、電池Ａ３を作製した。
【００３６】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏ代わりに、Ａｌ（ＮＨ4）（ＳＯ4）2・１２Ｈ2Ｏを用いた以外は、電池Ａ０と同様にして、電池Ａ４を作製した。
【００３７】
正極の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを混合して熱処理したＬｉＣｏＯ2を用いる代わりに、ＬｉＣｏＯ2を用いた以外は、電池Ａ０と同様にして比較電池Ｘ０を作製した。
【００３８】
上述の電池Ａ０〜Ａ４及び比較電池Ｘ０について、１０ｍＡの定電流で電池電圧４．２Ｖまで充電した後、放電抵抗１ｋΩで３．０Ｖに至るまで放電し、放電容量を測定した。次に、１０ｍＡの定電流で電池電圧４．２Vまで充電して、８０℃の恒温槽で６０日間保存した後、放電抵抗１ｋΩで電池電圧２．７Ｖまで放電して保存後の放電容量を測定し、下記の数１の式に基づいて自己放電率を算出した。その結果を下記の表１に示す。
【００３９】
【数１】
【００４０】
【表１】
【００４１】
表１より判るように、ＬｉＣｏＯ2に、ＡｌＫ（ＳＯ4）2、ＡｌＮａ（ＳＯ4）2、ＡｌＲｂ（ＳＯ4）2、ＡｌＣｓ（ＳＯ4）2、或いはＡｌ（ＮＨ4）（ＳＯ4）2を含有させた電池Ａ０〜Ａ４は、比較電池Ｘ０に比べ、自己放電率が大幅に小さく、保存特性に優れている。
【００４２】
（実験２）
正極活物質を作製する際のリチウム含有複合酸化物の種類について、下記の電池Ｂ２、Ｂ８〜Ｂ１３、Ｙ２、Ｙ８〜Ｙ１３を作製して検討を行った。
【００４４】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｃｏ0.5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ２を作製した。
【００５０】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｔｉ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ８を作製した。
【００５１】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｃｒ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ９を作製した。
【００５２】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｍｇ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ１０を作製した。
【００５３】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ａｌ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ１１を作製した。
【００５４】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｃｕ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ１２を作製した。
【００５５】
正極活物質の作製において、ＬｉＣｏＯ2を用いる代わりにＬｉＮｉ0.5Ｇａ0。5Ｏ2を用いる以外は、電池Ａ０と同様にして、電池Ｂ１３を作製した。
【００５６】
正極活物質の作製において、リチウム含有複合酸化物に対して、ＡｌＸ（ＳＯ4）2を含有させない以外は、電池Ｂ２、Ｂ８〜Ｂ１３と同様にして、比較電池Ｙ２、Ｙ８〜Ｙ１３を夫々作製した。
【００５７】
上述の電池Ｂ２、Ｂ８〜Ｂ１３及び比較電池Ｙ２、Ｙ８〜Ｙ１３について、自己放電率を算出した。その結果を表２に示す。尚、自己放電率の算出方法は、実験１と同じである。
【００５８】
【表２】
【００５９】
表２より判るように、電池Ｂ２、Ｂ８〜Ｂ１３は、比較電池Ｙ２、Ｙ８〜Ｙ１３に比べ、自己放電率が小さく、保存特性に優れている。即ち、ＬｉＮｉaＣｏbＭcＯ2（但し、０≦ａ＜１、０≦ｂ＜１、ａ＋ｂ＋ｃ＝１；０≦ｃ≦０．５；Ｍは、Ｔｉ、Ｃｒ、Ｍｇ、Ａｌ、Ｃｕ、Ｇａの中か選ばれる少なくとも一種）にＡｌＸ（ＳＯ4）2を含有させた活物質を正極に用いた非水電解液二次電池は、自己放電率が小さく、保存特性に優れていることが判る。
【００６０】
即ち、表１及び表２より、ＬｉＮｉaＣｏbＭcＯ2（但し、０≦ａ＜１、０≦ｂ＜１、ａ＋ｂ＋ｃ＝１；０≦ｃ≦０．５；Ｍは、Ｔｉ、Ｃｒ、Ｍｇ、Ａｌ、Ｃｕ、Ｇａの中か選ばれる少なくとも一種）に、ＡｌＫ（ＳＯ4）2、ＡｌＮａ（ＳＯ4）2、ＡｌＲｂ（ＳＯ4）2、ＡｌＣｓ（ＳＯ4）2、或いはＡｌ（ＮＨ4）（ＳＯ4）2を含有させた活物質を、非水電解液二次電池の正極に用いた場合、その非水電解液二次電池は、自己放電率が小さくなり、保存特性が向上することが明らかである。
【００６１】
（実験３（参考実験））
正極活物質におけるＡｌＸ（ＳＯ4）2の含有量について、下記の電池Ｃ１〜Ｃ１０を作製して検討を行った。
【００６２】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに１．２モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ１を作製した。
【００６３】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに１．５モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ２を作製した。
【００６４】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに２．５モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ３を作製した。
【００６５】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに３．０モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ４を作製した。
【００６６】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに７モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ５を作製した。
【００６７】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに１０モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ６を作製した。
【００６８】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに１２モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ７を作製した。
【００６９】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに１５モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ８を作製した。
【００７０】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに２０モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ９を作製した。
【００７１】
正極活物質の作製において、ＡｌＫ（ＳＯ4）2・１２Ｈ2Ｏを５モル％混合する代わりに２２モル％混合する以外は、電池Ａ０と同様にして、電池Ｃ１０を作製した。
【００７２】
正極活物質の作製において、硫酸コバルト水溶液と重炭酸ナトリウム水溶液を反応させ、沈殿を濾過、水洗、乾燥して得た塩基性炭酸コバルトを、４００℃で熱処理し、四三酸化コバルトを得た。この四三酸化コバルトを、炭酸リチウムと所定比で混合し、９００℃で反応させ、ＬｉＣｏＯ2（硫酸根０．８モル％含有；（ＳＯ4）2では０．４モル％に相当）を作製した。この正極活物質の作製以外は、電池Ａ０と同様にして、比較電池Ｚ１を作製した。尚、この比較電池Ｚ１は特開平９−２４５７８７号公報に示されている電池に相当する。
【００７３】
上述の電池Ａ０、Ｃ１〜Ｃ１０及び比較電池Ｘ０、Ｚ１について、自己放電率を算出した。その結果を表３に示す。尚、自己放電率の算出方法は、実験１と同じである。
【００７４】
【表３】
【００７５】
表３より判るように、ＡｌＫ（ＳＯ4）2の含有量が１．５モル％以上、２０モル％以下の場合、自己放電率が比較電池Ｘ０、Ｚ１と比べ急激に低下し、保存特性が良好である。特に、前述の含有量が３．０モル％以上、１０モル％以下では、自己放電率は一層低くなり、保存特性は一層良好となる。尚、ＡｌＫ（ＳＯ4）2の含有量が２２モル％の場合、自己放電率の低下が小さいのは、ＡｌＫ（ＳＯ4）2が不純物として働き、自己放電率が増加したものと考えられる。
【００７６】
また、ＡｌＫ（ＳＯ4）2に代えて、実験１で用いたＡｌＮａ（ＳＯ4）2、ＡｌＲｂ（ＳＯ4）2、ＡｌＣｓ（ＳＯ4）2、或いはＡｌ（ＮＨ4）（ＳＯ4）2を用いた場合、また、ＬｉＣｏＯ2に代えて、実験２で用いたリチウム含有複合酸化物ＬｉＮｉaＣｏbＭcＯ2（但し、０≦ａ＜１、０≦ｂ＜１、ａ＋ｂ＋ｃ＝１；０≦ｃ≦０．５；Ｍは、Ｔｉ、Ｃｒ、Ｍｇ、Ａｌ、Ｃｕ、Ｇａの中か選ばれる少なくとも一種）についても、ＡｌＸ（ＳＯ4）2の含有量について検討を行った結果、上述の表３と同様の結果が得られた。
【００７７】
（実験４（参考実験））
正極活物質を作製する際の熱処理温度について、下記の電池Ｄ１〜Ｄ５を作製して検討を行った。
【００７８】
正極活物質の作製において、２５０℃で熱処理する代わりに、８０℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ０を作製した。
【００７９】
正極活物質の作製において、２５０℃で熱処理する代わりに、１００℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ１を作製した。
【００８０】
正極活物質の作製において、２５０℃で熱処理する代わりに、１５０℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ２を作製した。
【００８１】
正極活物質の作製において、２５０℃で熱処理する代わりに、２００℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ３を作製した。
【００８２】
正極活物質の作製において、２５０℃で熱処理する代わりに、３００℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ４を作製した。
【００８３】
正極活物質の作製において、２５０℃で熱処理する代わりに、３５０℃で熱処理する以外は、電池Ａ０と同様にして、電池Ｄ５を作製した。
【００８４】
【表４】
【００８５】
表４より判るように、熱処理温度が１００℃以上、３００℃以下の範囲では、自己放電率の低下が大きく、保存特性が特に優れている。尚、これはＬｉＣｏＯ2の表面がＡｌＫ（ＳＯ4）2により良好に被覆され、ＬｉＣｏＯ2と電解液との反応が十分に抑制されるためと考えられる。
【００８６】
【発明の効果】
本発明によれば、非水電解液二次電池の正極活物質として用いた場合、前記二次電池を放置した際における放電容量の低下が少なく、二次電池の保存特性を良好にするのに適した活物質を提供し得る。
【００８７】
また、本発明によれば、非水電解液二次電池の正極として用いた場合、前記二次電池を放置した際における放電容量の低下が少なく、二次電池の保存特性を良好にするのに適した電極を提供し得る。
【００８８】
また、本発明によれば、放置した際における放電容量の低下が少なく、保存特性を良好にするのに適した非水電解液二次電池を提供し得る。
【００８９】
本発明によれば、非水電解液二次電池の正極活物質として用いた場合、前記二次電池を放置した際における放電容量の低下が少なく、二次電池の保存特性を良好にするのに適した活物質の製造方法を提供し得る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an active material suitable for use as a positive electrode of a nonaqueous electrolyte secondary battery, an electrode having the active material, a nonaqueous electrolyte secondary battery using the electrode, and a method for producing the active material.
[0002]
[Prior art]
Conventionally, some non-aqueous electrolyte secondary batteries include a positive electrode and a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte.
[0003]
Such a non-aqueous electrolyte secondary battery uses, as a positive electrode active material, a lithium-containing composite oxide that is a composite oxide of lithium and a metal such as nickel or cobalt, and has a voltage of about 4V. Due to its high capacity, active research and development is underway.
[0004]
However, the conventional non-aqueous electrolyte secondary battery described above has a problem that storage characteristics deteriorate due to a reaction between the positive electrode and the electrolyte during storage.
[0005]
In order to solve such a problem, for example, JP-A-9-245787 has proposed a positive electrode active material containing sulfate radical (SO 4 ).
[0006]
However, even in a non-aqueous electrolyte secondary battery using such a positive electrode active material, the discharge capacity is reduced and the storage characteristics are not satisfactory.
[0007]
[Means for Solving the Problems]
Active material of the present invention, LiNi a Co b M c O 2 ( where, 0 ≦ a <1,0 ≦ b <1, a + b + c = 1; 0 ≦ c ≦ 0.5; M is, Ti, Cr, Mg 1.5 mol of AlX (SO 4 ) 2 (X is at least one selected from Na, K, Rb, Cs, NH 4 ) with respect to at least one selected from Al, Cu, and Ga ). % Or more and 20 mol% or less, and heat-treated at 80 ° C. or more and 350 ° C. or less .
[0008]
In addition, the present invention, when used as a positive electrode of a non-aqueous electrolyte secondary battery, has a small decrease in discharge capacity when the secondary battery is left, and is suitable for improving the storage characteristics of the secondary battery. The object is to provide an electrode.
[0009]
Another object of the present invention is to provide a non-aqueous electrolyte secondary battery suitable for improving storage characteristics with little reduction in discharge capacity when left untreated.
[0010]
In addition, when the present invention is used as a positive electrode active material of a non-aqueous electrolyte secondary battery, there is little decrease in discharge capacity when the secondary battery is left, and the secondary battery has good storage characteristics. An object of the present invention is to provide a method for producing a suitable active material.
[0011]
[Means for Solving the Problems]
Active material of the present invention, LiNi a Co b M c O 2 ( where, a + b + c = 1 ; 0 ≦ c ≦ 0.5; M is, Mn, Fe, Zn, Ti , Cr, Mg, Al, Cu, Ga At least one selected from the group consisting of AlX (SO 4 ) 2 (X is at least one selected from Na, K, Rb, Cs, and NH 4 ).
[0012]
When such an active material is used as the positive electrode active material of a non-aqueous electrolyte secondary battery, the secondary battery has a low self-discharge rate and the storage characteristics of the secondary battery are improved. Note that this is, LiNi a Co b active portion of M c O 2 is reduced, the reaction between the positive electrode active material and the electrolytic solution is suppressed, is considered to be because the degradation of the positive electrode is suppressed. Further, depending on the amount of M added to LiNi a Co b M c O 2 , the charge / discharge capacity may decrease, and the amount of M added is preferably in the range of 0 ≦ c ≦ 0.5.
[0013]
Furthermore, in the active material of the present invention, when the content of the AlX (SO 4 ) 2 is 1.5 mol% or more and 20 mol% or less with respect to the LiNi a Co b M c O 2 , When used as a positive electrode active material for an electrolyte secondary battery, the self-discharge rate of the secondary battery is significantly reduced.
[0014]
Furthermore, in the active material of the present invention, the content of the AlX (SO 4 ) 2 is 3 mol% or more and 10 mol% or less with respect to the LiNi a Co b M c O 2 . When used as a positive electrode active material for a secondary battery, the self-discharge rate of the secondary battery is further greatly reduced.
Moreover, the active material of this invention WHEREIN: When the said heat processing temperature is 100 degreeC or more and 300 degrees C or less, the self-discharge rate of a secondary battery falls significantly.
[0015]
Moreover, since the AlX (SO 4 ) 2 coats the surface of the LiNi a Co b M c O 2 , the active material of the present invention has a sufficient reaction between the LiNi a Co b M c O 2 and the electrolyte. It is suppressed.
[0016]
The electrode of the present invention is characterized by having the above-described active material.
[0017]
When the electrode having such a configuration is used as a positive electrode of a non-aqueous electrolyte secondary battery, the self-discharge rate of the secondary battery is small, and the storage characteristics of the secondary battery are improved.
[0018]
The non-aqueous electrolyte secondary battery of the present invention is characterized by using the above electrode as a positive electrode.
[0019]
The non-aqueous electrolyte secondary battery having such a configuration has a small self-discharge rate and good storage characteristics.
[0020]
In addition, as a solute of the electrolyte solution of the non-aqueous electrolyte secondary battery of the present invention, LiPF 6 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiCF 3 (CF 2 ) 3 SO 3 or the like can be used, but is not limited to this.
[0021]
In addition, as a solvent for the electrification solution of the non-aqueous electrolyte secondary battery of the present invention, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, sulfolane, 1,2-dimethoxyethane, tetrahydrofuran, 1,3- Although dioxolane etc. can be used, it is not limited to this.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0026]
[Preparation of positive electrode active material]
AlK (SO 4 ) 2 .12H 2 O was mixed with LiCoO 2 at 5 mol% and heat-treated at 250 ° C. for 2 hours to prepare a positive electrode active material.
[0027]
[Preparation of positive electrode]
The positive electrode active material, carbon powder as a conductive agent, and polytetrafluoroethylene as a binder were mixed at a weight ratio of 80:10:10 to obtain a positive electrode mixture.
[0028]
Next, this mixture was pressure-molded and vacuum-dried at 100 ° C. for 2 hours to produce a positive electrode.
[0029]
[Preparation of negative electrode]
A lithium-aluminum alloy was punched out to a predetermined size to produce a negative electrode.
[0030]
[Preparation of electrolyte]
LiPF 6 was dissolved at a ratio of 1M in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 to prepare an electrolytic solution.
[0031]
[Battery assembly]
A positive electrode having a substantially U-shaped cross section in which the negative electrode is fixed to an inner bottom surface of a negative electrode can having a substantially U-shaped cross section, and the positive electrode is fixed via a separator impregnated with an electrolyte prepared in the volume ratio described above. A can was placed to produce Battery A0. As the separator, an ion-permeable polypropylene microporous membrane was used.
[0032]
(Experiment 1 (Reference Experiment) )
The types of AlX (SO 4 ) 2 contained in the positive electrode active material were examined by producing the following batteries A1 to A4.
[0033]
In preparing the positive electrode active material, AlK (SO 4) to 2 · 12H 2 O Instead, except for using AlNa (SO 4) 2 · 12H 2 O , in the same manner as the battery A0, a battery was prepared A1.
[0034]
In preparing the positive electrode active material, AlK (SO 4) to 2 · 12H 2 O Instead, except for using AlRb (SO 4) 2 · 12H 2 O , in the same manner as the battery A0, a battery was prepared A2.
[0035]
In preparing the positive electrode active material, AlK (SO 4) to 2 · 12H 2 O Instead, except for using AlCs (SO 4) 2 · 12H 2 O , in the same manner as the battery A0, a battery was prepared A3.
[0036]
The battery A4 was prepared in the same manner as the battery A0 except that Al (NH 4 ) (SO 4 ) 2 · 12H 2 O was used instead of AlK (SO 4 ) 2 · 12H 2 O in the production of the positive electrode active material. Produced.
[0037]
In the preparation of the positive electrode, instead of using AlK (SO 4) 2 · 12H 2 LiCoO 2 which O was mixed and heat treated, except that LiCoO 2 was used was prepared comparative battery X0 in the same manner as the battery A0.
[0038]
The batteries A0 to A4 and the comparative battery X0 were charged to a battery voltage of 4.2 V with a constant current of 10 mA, then discharged to 3.0 V with a discharge resistance of 1 kΩ, and the discharge capacity was measured. Next, after charging to a battery voltage of 4.2 V at a constant current of 10 mA and storing it in a constant temperature bath at 80 ° C. for 60 days, discharging to a battery voltage of 2.7 V with a discharge resistance of 1 kΩ and measuring the discharge capacity after storage The self-discharge rate was calculated based on the following equation (1). The results are shown in Table 1 below.
[0039]
[Expression 1]
[0040]
[Table 1]
[0041]
As can be seen from Table 1, in LiCoO 2 , AlK (SO 4 ) 2 , AlNa (SO 4 ) 2 , AlRb (SO 4 ) 2 , AlCs (SO 4 ) 2 , or Al (NH 4 ) (SO 4 ) 2 In comparison with the comparative battery X0, the batteries A0 to A4 containing the battery have a significantly lower self-discharge rate and excellent storage characteristics.
[0042]
(Experiment 2)
The following batteries B2, B8 to B13 , Y2, and Y8 to Y13 were prepared and examined with respect to the types of lithium-containing composite oxides when the positive electrode active material was prepared.
[0044]
In the preparation of the positive electrode active material, except that the LiNi 0.5 Co 0.5 O 2 instead of using LiCoO 2, similarly to the battery A0, a battery was prepared B2.
[0050]
Instead of using LiCoO 2 in the production of the positive electrode active material, LiNi 0.5 Ti 0 . A battery B8 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0051]
Instead of using LiCoO 2 in the production of the positive electrode active material, LiNi 0.5 Cr 0 . A battery B9 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0052]
Instead of using LiCoO 2 in the production of the positive electrode active material, LiNi 0.5 Mg 0 . A battery B10 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0053]
Instead of using LiCoO 2 in the production of the positive electrode active material, LiNi 0.5 Al 0 . A battery B11 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0054]
Instead of using LiCoO 2 in the production of the positive electrode active material, LiNi 0.5 Cu 0 . A battery B12 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0055]
LiNi 0.5 Ga 0 instead of using LiCoO 2 in the production of the positive electrode active material. A battery B13 was produced in the same manner as the battery A0, except that 5 O 2 was used.
[0056]
Comparative batteries Y2 and Y8 to Y13 were prepared in the same manner as batteries B2 and B8 to B13, respectively , except that in the production of the positive electrode active material, AlX (SO 4 ) 2 was not contained in the lithium-containing composite oxide. .
[0057]
Self-discharge rates were calculated for the above-described batteries B2, B8 to B13 and comparative batteries Y2, Y8 to Y13 . The results are shown in Table 2. The method for calculating the self-discharge rate is the same as in Experiment 1.
[0058]
[Table 2]
[0059]
As can be seen from Table 2, the batteries B2 and B8 to B13 have a smaller self-discharge rate and excellent storage characteristics than the comparative batteries Y2 and Y8 to Y13 . That, LiNi a Co b M c O 2 ( where, 0 ≦ a <1,0 ≦ b <1, a + b + c = 1; 0 ≦ c ≦ 0.5; M is, Ti, Cr, Mg, Al , Cu, A non-aqueous electrolyte secondary battery using an active material containing AlX (SO 4 ) 2 in at least one selected from Ga ) as a positive electrode has a low self-discharge rate and excellent storage characteristics. I understand.
[0060]
That is, from Table 1 and Table 2, LiNi a Co b M c O 2 ( where, 0 ≦ a <1,0 ≦ b <1, a + b + c = 1; 0 ≦ c ≦ 0.5; M is, Ti, Cr , Mg, Al, Cu, Ga ), AlK (SO 4 ) 2 , AlNa (SO 4 ) 2 , AlRb (SO 4 ) 2 , AlCs (SO 4 ) 2 , or Al (NH 4 ) When an active material containing (SO 4 ) 2 is used for the positive electrode of a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery has a reduced self-discharge rate and improved storage characteristics. It is clear to do.
[0061]
(Experiment 3 (Reference Experiment) )
Regarding the content of AlX (SO 4 ) 2 in the positive electrode active material, the following batteries C1 to C10 were prepared and examined.
[0062]
A battery C1 was produced in the same manner as the battery A0 except that, in the production of the positive electrode active material, 1.2 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0063]
A battery C2 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 1.5 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0064]
A battery C3 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 2.5 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0065]
A battery C4 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 3.0 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0066]
A battery C5 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 7 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0067]
A battery C6 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 10 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0068]
A battery C7 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 12 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0069]
A battery C8 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 15 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0070]
A battery C9 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, 20 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0071]
A battery C10 was produced in the same manner as the battery A0, except that in the production of the positive electrode active material, 22 mol% was mixed instead of 5 mol% of AlK (SO 4 ) 2 .12H 2 O.
[0072]
In preparation of the positive electrode active material, a basic cobalt carbonate obtained by reacting a cobalt sulfate aqueous solution and a sodium bicarbonate aqueous solution, filtering the precipitate, washing with water and drying was heat-treated at 400 ° C. to obtain cobalt trioxide. This cobalt trioxide is mixed with lithium carbonate at a predetermined ratio and reacted at 900 ° C. to produce LiCoO 2 (containing 0.8 mol% sulfate radical; equivalent to 0.4 mol% in (SO 4 ) 2 ). did. A comparative battery Z1 was produced in the same manner as the battery A0 except that this positive electrode active material was produced. The comparative battery Z1 corresponds to the battery disclosed in Japanese Patent Laid-Open No. 9-245787.
[0073]
Self-discharge rates were calculated for the batteries A0 and C1 to C10 and the comparative batteries X0 and Z1. The results are shown in Table 3. The method for calculating the self-discharge rate is the same as in Experiment 1.
[0074]
[Table 3]
[0075]
As can be seen from Table 3, when the content of AlK (SO 4 ) 2 is 1.5 mol% or more and 20 mol% or less, the self-discharge rate is drastically decreased as compared with comparative batteries X0 and Z1, and the storage characteristics It is good. In particular, when the content is 3.0 mol% or more and 10 mol% or less, the self-discharge rate is further lowered and the storage characteristics are further improved. In addition, when the content of AlK (SO 4 ) 2 is 22 mol%, the decrease in the self-discharge rate is small because AlK (SO 4 ) 2 acts as an impurity and the self-discharge rate is increased.
[0076]
In place of AlK (SO 4 ) 2 , AlNa (SO 4 ) 2 , AlRb (SO 4 ) 2 , AlCs (SO 4 ) 2 , or Al (NH 4 ) (SO 4 ) 2 used in Experiment 1 is used. If used, also, in place of LiCoO 2, lithium-containing composite oxide was used in experiment 2 LiNi a Co b M c O 2 ( where, 0 ≦ a <1,0 ≦ b <1, a + b + c = 1; 0 ≦ c ≦ 0.5; M is at least one selected from Ti, Cr, Mg, Al, Cu, and Ga ). As a result of examining the content of AlX (SO 4 ) 2 , Similar results as in Table 3 were obtained.
[0077]
(Experiment 4 (Reference Experiment) )
The following battery D1-D5 was produced and examined about the heat processing temperature at the time of producing a positive electrode active material.
[0078]
A battery D0 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 80 ° C. instead of heat treatment at 250 ° C.
[0079]
A battery D1 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 100 ° C. instead of heat treatment at 250 ° C.
[0080]
A battery D2 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 150 ° C. instead of heat treatment at 250 ° C.
[0081]
A battery D3 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 200 ° C. instead of heat treatment at 250 ° C.
[0082]
A battery D4 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 300 ° C. instead of heat treatment at 250 ° C.
[0083]
A battery D5 was produced in the same manner as the battery A0 except that in the production of the positive electrode active material, heat treatment was performed at 350 ° C. instead of heat treatment at 250 ° C.
[0084]
[Table 4]
[0085]
As can be seen from Table 4, when the heat treatment temperature is in the range of 100 ° C. or higher and 300 ° C. or lower, the self-discharge rate is greatly reduced and the storage characteristics are particularly excellent. This is presumably because the surface of LiCoO 2 is satisfactorily covered with AlK (SO 4 ) 2 and the reaction between LiCoO 2 and the electrolyte is sufficiently suppressed.
[0086]
【The invention's effect】
According to the present invention, when used as a positive electrode active material for a non-aqueous electrolyte secondary battery, there is little decrease in discharge capacity when the secondary battery is left, and the storage characteristics of the secondary battery are improved. A suitable active material can be provided.
[0087]
In addition, according to the present invention, when used as a positive electrode of a non-aqueous electrolyte secondary battery, there is little decrease in discharge capacity when the secondary battery is left, and the storage characteristics of the secondary battery are improved. A suitable electrode can be provided.
[0088]
In addition, according to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery suitable for improving storage characteristics with little reduction in discharge capacity when left untreated.
[0089]
According to the present invention, when used as a positive electrode active material for a non-aqueous electrolyte secondary battery, there is little decrease in discharge capacity when the secondary battery is left, and the storage characteristics of the secondary battery are improved. A method for producing a suitable active material can be provided.
Claims (6)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17697499A JP3649953B2 (en) | 1999-06-23 | 1999-06-23 | Active material, electrode, non-aqueous electrolyte secondary battery, and method for producing active material |
| US09/597,095 US6368749B1 (en) | 1999-06-23 | 2000-06-20 | Active substances, electrodes, nonaqueous electrolyte secondary cells, and a process for fabricating the active substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17697499A JP3649953B2 (en) | 1999-06-23 | 1999-06-23 | Active material, electrode, non-aqueous electrolyte secondary battery, and method for producing active material |
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| Publication Number | Publication Date |
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| JP2001006672A JP2001006672A (en) | 2001-01-12 |
| JP3649953B2 true JP3649953B2 (en) | 2005-05-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP17697499A Expired - Fee Related JP3649953B2 (en) | 1999-06-23 | 1999-06-23 | Active material, electrode, non-aqueous electrolyte secondary battery, and method for producing active material |
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| US (1) | US6368749B1 (en) |
| JP (1) | JP3649953B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8241791B2 (en) | 2001-04-27 | 2012-08-14 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
| KR20160033003A (en) * | 2014-09-17 | 2016-03-25 | 주식회사 엘지화학 | Cathode active material, and a lithium secondary battery comprising the same |
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| JP4995382B2 (en) * | 2001-07-05 | 2012-08-08 | 日本化学工業株式会社 | Lithium cobalt complex oxide, method for producing the same, lithium secondary battery positive electrode active material, and lithium secondary battery |
| JP4635386B2 (en) * | 2001-07-13 | 2011-02-23 | 株式会社Ｇｓユアサ | Positive electrode active material and non-aqueous electrolyte secondary battery using the same |
| US20030108793A1 (en) * | 2001-08-07 | 2003-06-12 | 3M Innovative Properties Company | Cathode compositions for lithium ion batteries |
| WO2003038931A1 (en) * | 2001-10-29 | 2003-05-08 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| US20040121234A1 (en) * | 2002-12-23 | 2004-06-24 | 3M Innovative Properties Company | Cathode composition for rechargeable lithium battery |
| DE602004017798D1 (en) * | 2003-02-21 | 2009-01-02 | Toyota Motor Co Ltd | Active material for the positive electrode of a nonaqueous electrolyte secondary battery |
| US7211237B2 (en) * | 2003-11-26 | 2007-05-01 | 3M Innovative Properties Company | Solid state synthesis of lithium ion battery cathode material |
| WO2011125722A1 (en) | 2010-04-01 | 2011-10-13 | 三菱化学株式会社 | Positive electrode material for lithium secondary battery, method for producing the same, positive electrode for lithium secondary battery, and lithium secondary battery |
| JP5152246B2 (en) * | 2010-04-23 | 2013-02-27 | 株式会社豊田自動織機 | Cathode active material for lithium ion secondary battery and lithium ion secondary battery |
| CA2916900C (en) | 2013-07-09 | 2018-12-11 | Dow Global Technologies Llc | Mixed positive active material comprising lithium metal oxide and lithium metal phosphate |
| JP2017500685A (en) | 2013-10-24 | 2017-01-05 | ダウ グローバル テクノロジーズ エルエルシー | Improved lithium metal oxide cathode materials and methods for making them |
| JP6835593B2 (en) | 2014-05-27 | 2021-02-24 | ダウ グローバル テクノロジーズ エルエルシー | Improved Lithium Metal Oxide Cathode Materials and Their Fabrication Methods |
| CN107004856B (en) | 2014-12-18 | 2021-06-04 | 陶氏环球技术有限责任公司 | Lithium ion battery with improved thermal stability |
| CN110707298B (en) * | 2018-07-10 | 2021-11-12 | 比亚迪股份有限公司 | Cathode material, preparation method thereof, lithium ion battery and vehicle |
| CN110707296B (en) * | 2018-07-10 | 2021-05-14 | 比亚迪股份有限公司 | Cathode material, preparation method thereof, lithium ion battery and vehicle |
| CN110707297B (en) * | 2018-07-10 | 2021-05-14 | 比亚迪股份有限公司 | Cathode material, preparation method thereof, lithium ion battery and vehicle |
| FI3994749T3 (en) * | 2019-07-03 | 2023-06-28 | Umicore Nv | Lithium nickel manganese cobalt composite oxide as a positive electrode active material for rechargeable lithium ion batteries |
| JP7477539B2 (en) * | 2019-07-03 | 2024-05-01 | ユミコア | Lithium nickel manganese cobalt composite oxide as a positive electrode active material for rechargeable lithium-ion batteries |
| TWI747735B (en) | 2021-02-08 | 2021-11-21 | 台灣立凱電能科技股份有限公司 | Particle structure of cathode material and manufacturing method thereof |
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| US5034291A (en) * | 1989-08-16 | 1991-07-23 | Rayovac Corporation | Aluminum compound additives to reduce zinc corrosion in anodes of electrochemical cells |
| JP3192945B2 (en) | 1995-10-13 | 2001-07-30 | 三洋電機株式会社 | Lithium secondary battery |
| JPH09245787A (en) | 1996-03-07 | 1997-09-19 | Kansai Shokubai Kagaku Kk | Positive electrode active material for lithium secondary battery |
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- 1999-06-23 JP JP17697499A patent/JP3649953B2/en not_active Expired - Fee Related
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8241791B2 (en) | 2001-04-27 | 2012-08-14 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
| US8685565B2 (en) | 2001-04-27 | 2014-04-01 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
| KR20160033003A (en) * | 2014-09-17 | 2016-03-25 | 주식회사 엘지화학 | Cathode active material, and a lithium secondary battery comprising the same |
| KR101868663B1 (en) * | 2014-09-17 | 2018-06-18 | 주식회사 엘지화학 | Cathode active material, and a lithium secondary battery comprising the same |
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| US6368749B1 (en) | 2002-04-09 |
| JP2001006672A (en) | 2001-01-12 |
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